Method of preparing a complex fertilizer comprising urea coated with ammonium phosphate



nited States Patent Olfice Patented Feb. 4, 1969 3,425,319 The first step of the process is the ammoniation or g g gg partial neutralization of wet process phosphoric acid. Wet

AMMONIUM PHOSPHATE process phosphoric ac1d 1s usually obtamed by the acidulation of phosphate rock with sulfuric acid and then separat- L WIS Arthur Barr W1] ette Ill. nd Elm J. Arveson Carlos, can? g assaignor toeimemafionai 5 mg the supernatant llquid from the sol1ds formed, e.g.,

Minerals & Chemical Corporation, a corporation of calcium sulfate. The wet process phosphoric acid contains N Y k, id Arveson i to Chevron R numerous trace elements. These include H011 and alumisearch Company, San Francisco, Calif., a corporation num. While on the one hand the trace elements increase of Delaware the nutrient value of the fertilizer for plants, the presence No Drawing. Filed May 24, 1965, Ser. No. 458,423 US. CI. 71-29 Int. Cl. C05c 9/00 10 of the trace elements interfere with maintaining flowa'ble 4 Clalms slurries when ammoniating the wet process phosphoric acid. The trace metals form thixotropic salts which set up the mixture of monoand diammonium phosphates as hard nonflowable colloids. This problem is avoided by the ABSTRACT OF THE DISCLOSURE present process High nitrogen content fertilizers are prepared by coating The wet process phosphoric acid used should have at urea prills with an ammonium phosphate composition in least 39% P 0 (weight percent of P 0 present in the the presence of ammonia and then drying the resulting aqueous mixture. While Wet process phosphoric acid havgranules. ing concentrations as high as 54% P 0 may be used,

these should be diluted down with water to about 40 to This invention concerns an improved method for the 45 P205 prefprably the wet process phosphonc ac1d preparation of a complex fertilizer. More particularly, this as Introduced i have from about 40 to 4 P 9 invention concerns an improved method for the prepara- The ammorila and Wet Process phosphonc i 13 tion of a complex fertilizer which contains urea as the efany l slmulianeollsly to a vessel usuiilny m the demajor nitrogen Soumi sired stoichiometric rat1o. The heat resultlng from the B ecause of the high percentage of available nitrogen neutralization of phosphoric ac1d W111 usually be suffic ent in urea, it is a particularly desirable component for fertilto niamtam the temperatl'ue m range of .about 220 izers. Urea is readily available from the reaction of car- 3 preferably 235 to 245 Sufliclent ammqma bon dioxide and ammonia. However, in the presence of 1S add.ed to q an aqueous Shiny of monoammomum water at elevated temperatures, particularly at high or 10W (ilammomum Phosphate havmg an NH3:H3PO4 mole pH, urea is readily hydrolyzed to its components resultratlo m the range of preferably to 2 ing in a significant economic loss. Furthermore, during the The PH of the resultmg aqueous Slurry W111 be m the 5.5 to 6.5 desirabl in the range of about manufacture of the fert1l1zer, biuret may be formed WhlCh range of about y o is toxic to plants and therefore undesirable. Urea sulfers 5 $1 4 2- t l slf g avlty iat flbtillt 5,01 W11} 2? from the further disadvantage of being hygroscopic and 35 on grams per m era to caking when Storei g./ ml. The Weight percent of water wlll be in the range of In order to prepare a satisfactory solid granular comg 15 to g ig 8 M d plex fertilizer incorporating urea, it is necessary to mini- 6 aqueous s uny escn e a eve 1S pumpa e mize the hydrolysis of the urea during the formation of fiowable and can transferrid by pumpmg or glavlty the complex fertilizer and to avoid, completely if possible, 40 flow the i f g amllmmawr' the formation of biuret. Furthermore, it is essential that granu. ator t e urea pm S are coaie Wlt a mlxture as the urea be almost completely coated with a nonhygrodescnged above of fi Eammonmm phosphate scopic coating so that the fertilizer does not cake on and e monoainmomufn p osp ate reacted Wlth Storage. monia to form drammomum phosphate.

Pursuant to this invention, complex solid granular ferd The fi i 2 9 i bilislcany i g tilizers are prepared containing urea as their major nitro- 1 i f i m 0 h 2 w l z gen source by spraying onto a rolling bed of urea prills 9 r 16 (We e e para to e and fertilizer fines an aqueous slurry of monoand diamrun} 5 i a P1P e wlth a plurahty of holes which Serves monium phosphate having an NH3:H3P04 mole ratio in to dlstrlbute the flurry of monoammonlum and dlammoa narrow range, in the presence of ammonia vapor in mum phosphates as fine i f Onto Under h stoichiometric excess over the amount required to change l parallel to the first P 1p 18 another p 1p 6 having a thm all of the ammonium phosphate to diammonium phosi throughlmt most Its length a Plurahty i Open" phate and then y g the granules to a desired moisture mgsfor the IIIlIIOdIICtIOII Of ammonia vapor. The slit serves conteilt and recycling a portion of the granules as fines. to distrlbute the ammonla vapor relatlvely evenly throughout the bed of solid particles. gg fifg W111 be consldered accordmg to the follow' The urea prills which are introduced into the ammoniator-granulator will generally be only a portion of (I) Ammoniation of wet process phosphoric acid: the solid particles introduced. The size of the urea prills is (A) Wet process phosphoric acid critical to the proper preparation of granular particles. (B) Ammoniating conditions The prills should be of a mesh size in the range of (C) Characteristics of the aqueous slurry 6+60, preferably 6+20 Tyler mesh. The prills should (II) Coating of urea prills: have an average diameter in the range of about 0.032 to (A) Description of coating equipment 0.040 inch. (B) Description of urea prills Other solids introduced to maintain the bed will be (C) Presence of other materials 5 recycled fines. That is, particles which have been formed (D) Ammoniating conditions and were too small or too large as compared to the de- (E) Temperature and other conditions sired size granule. The oversized particles are ground to (F) Description of product form fines. Also, inert earths or other inert material may (III) Drying and sizing: be added as desired. The size of the fines and the inert (A) Drying conditions filler will be not larger than the urea prills and preferably (B) Sizing smaller than the urea prills. That is, the average diameter (C) Miscellaneous will be preferably less than 0.032.

The ammonia vapor introduced should be in significant excess of the amount required for the formation of the diammonium phosphate from the monoammonium phosphate present. The excess ammonia should be at least 20% greater than stoichiometric and desirable in the range of 25 to 100% greater. While even greater excesses of ammonia vapor may be used, it is found that no advantage is obtained and the loss of ammonia is uneconomical.

The ratio of urea prills to other solids-fertilizer fines and inert filler, when presentas well as to the aqueous slurry, is critical to the preparation of properly coated urea, with a minimum of both hydrolysis and formation of biuret. Depending on the ultimate composition of the fertilizer, about 0.5 to 1 part of urea will be introduced per part of slurry, and about 5 parts to 8 parts of recycled fines per part of slurry. In addition, from to 1 part of filler per part of slurry may also be added.

The temperature in the ammoniator-granulator will be in the range of about 120 to 180 F., desirably 140 to 160 F. The heat from the neutralization will usually be sufficient to maintain this temperature. However, external heat may be required.

The particles or granules coming out of the ammoniator-granulator will, for the most part, be hard round particles having urea cores surrounded by a coating of diammonium phosphate. They will usually have about 3 to 6 weight percent of water and will require further drying. The fertilizer units as N and P 0 will generally be at least about 40 and may be 60 or higher.

The solid granules are then transferred to a drier which is operated at a temperature in the range of 140 to 200 F. The residence time for the particles in the drier will be in the range of about 5 to 60 minutes.

The particles are now sized by means of screens. The undersized or fines are recycled back to the ammoniatorgranulator along with the pulverized oversized particles. The screening of the particles is carried out at elevated temperatures, preferably in the range of about 125 to 185 F. The material which is returned to the ammoniatorgranulator is referred to as recycled fines.

The moisture content of the final product will generally be in the range of about 1 to 3 weight percent. The amount of material returned as recycled fines will usually be about 50 to 85 weight percent of the product withdrawn from the drier.

The product as obtained has less than 1% of biuret and at least 90% of the P 0 is water soluble. The water solubility is desirable for a satisfactory fertilizer in order to make the phosphorus available to the plants. The urea is at least 60% and generally 65 to 80% of the available nitrogen.

The following example illustrates a typical preparation of :20:0 NPK fertilizer.

Into a vessel (neutralizer) was introduced phosphoric acid (47.1% P 0 at a rate of 430 lbs./hr., liquid ammonia at a rate of 67 lbs./hr., and water at a rate of 57 lbs./hr. The temperature in the reactor was maintained at about 240 F. The slurry which overfiowed the reactor had a pH of about 6 and a specific gravity of about 1.8 g./ml. Its composition was 11.45% ammoniacal nitrogen, 42.01% P 0 and 17.1% water.

The overflow from the neutralizer was transferred to the ammoniator-granulator and sprayed directly onto a bed of rolling fines-urea prills, recycled fines, inert filler. The bed of fines was maintained by introducing urea prills at a rate of 287 lbs/hr. (12|20 Tyler mesh), recycled fines at a rate of 2,430 lbs/hr. (12 Tyler mesh) and inert filler at the rate of 295 lbs/hr. Ammonia was fed into the ammoniator at a rate of lbs./ hr. (34% excess over that required for formation of diammonium phosphate from the monoammonium phosphate present). The temperature in the ammoniator was about 140-150 F.; the granules withdrawn from the ammoniator had a discharge temperature of about 153 F. The composition was 5.29% ammoniacal nitrogen, 17.64% urea nitrogen,

4 16.44% P 0 and 3.22% water. 33.5% of the particles had a mesh size in the range of 6+l2.

The particles were then dried in a drier in which the inlet air temperature was about 250 to 350 F. and the exit temperature of the particles about 175 F. The moisture content of the particles was about 1.7%. The particles were then separated by means of screens; the particles having the desired mesh size (6+12) had the following composition: 6.91% ammoniacal nitrogen, 13.6% urea nitrogen, 20.52% P 0 and 1.68% water. The P 0 was 93.3% water soluble, and the amount of biuret was less than 1%. Hydrolysis of the urea was less than 5%.

It is evident from the foregoing that by using only a partially neutralized wet process phosphoric acida mixture of monoand diammonium phosphate with a narrow ammonia to H PO mole ratio-to coat urea prills in the presence of large amounts of fines, composed of fertilizer having the desired composition, at a specified temperature range and in the presence of a relatively large excess of ammonia vapor, the formation of biuret is minimized, the loss of urea by hydrolysis is almost completely avoided, and a fertilizer having substantially all of the phosphorus and nitrogen available to the plant is obtained.

As will be evident to those skilled in the art, various modifications on this process can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

We claim: 1. A method for preparing complex fertilizer having urea as its major nitrogen source, which comprises:

in a reaction zone spraying onto a rolling bed of urea prills and recycled fines an aqueous slurry consisting essentially of monoand diammonium phosphate in an ammonia atmosphere at a temperature in the range of about to 200 F.;

drying the resulting granules at a temperature in the range of 140 to 200 F. for a time sufficient to lower the moisture content below 3 weight percent;

screening the material from the drier, separating the desired size granules from the oversized and undersized particles, pulverizing the oversized particles and combining the pulverized particles with the undersized particles to be used as said recycled fines;

wherein the aqueous slurry has an NH to H PO mole ratio in the range of 1.3 to 1.4 and a P 0 content of from 40 to 45 weight percent;

the urea prills have an average size in the range of about 6+60 mesh and the recycled fines are of not greater size than said urea prills; and

the weight ratio of addition to the reaction zone of aqueous slurry, urea prills, recycled fines and ammonia is 1:0.5-1:58:0.1-0.3, respectively, wherein the amount of ammonia is in at least 20% excess of that required to transform all of the monoammonium phosphate to diammonium phosphate.

2. A method according to claim 1, wherein the NH to H PO mole ratio in the aqueous slurry is 1.32 to 1.35 and the aqueous slurry has 40 to 42% P 0 3. A method according to claim 1, wherein the urea prills are of a mesh size of 6+20.

4. A fertilizer composition prepared as described in claim 1.

References Cited UNITED STATES PATENTS 3,333,939 8/1967 Davis et a1. 7129 DONALL H. SYLVESTER, Primary Examiner.

R. D. BAJEFSKY, Assistant Examiner.

US. Cl. X.R. 

